The invention relates to compositions for the oxidation dyeing of keratin fibres, comprising at least one oxidation base and at least one coupler chosen from indolizine derivatives comprising at least one cationic group Z, wherein Z may be chosen from quaternized aliphatic chains, aliphatic chains comprising at least one quaternized saturated ring, and aliphatic chains comprising at least one quaternized unsaturated ring, to oxidation dyeing processes using them and to novel cationic indolizine derivatives.
Dye compositions comprising oxidation dye precursors are known in the art for dyeing keratinous fibres, such as human hair. The oxidation dye precursors include ortho-phenylenediamines, para-phenylenediamines, ortho-aminophenols, para-aminophenols, and heterocyclic compounds. These are generally known as oxidation bases. The oxidation dye precursors, i.e., oxidation bases, are generally colorless or weakly colored compounds which may give rise to colored compounds and dyes when combined with oxidizing products via oxidative coupling.
The shades obtained with these oxidation bases may be varied by combining them with couplers or coloration modifiers. Such coloration modifiers may, for example, be chosen from aromatic meta-diamines, meta-aminophenols, meta-diphenols, and certain heterocyclic compounds, such as indole compounds.
The variety of molecules used as oxidation bases and couplers may make it possible to obtain a wide range of colours.
The so-called xe2x80x9cpermanentxe2x80x9d coloration obtained from using these oxidation dyes should have at least one of the following desirable characteristics. The coloration should have no toxicological drawbacks, the shades obtained should have the desired intensity, and the coloration should have good resistance to external agents to which the fibres may be subjected, such as light, bad weather, washing, permanent-waving, perspiration, and rubbing. The dyes should allow coverage of white hairs, and should be as unselective as possible, that is, they should allow only the smallest possible differences in coloration along the same keratin fiber, which may be differently sensitized (i.e. damaged) between its end tip and its root.
Indazole-type compounds have been used in the field of hair dyeing. For example, in DE-A-1 492 166, the disclosure of which is incorporated herein by reference, the polycondensation of such compounds via oxidation has been proposed; in DE-A-2 623 564, the disclosure of which is incorporated herein by reference, it has been proposed to combine hydroxy-indazoles with tetraaminopyrimidines, and in U.S. Pat. No. 4,013,404, the disclosure of which is incorporated herein by reference, certain aminoindazoles and their use as oxidation dye precursors have been proposed.
The inventors have discovered, entirely surprisingly and unexpectedly, that the indolizine derivatives of formula (I) defined below comprising at least one cationic group Z, Z being chosen from quaternized aliphatic chains, aliphatic chains comprising at least one quaternized saturated ring and aliphatic chains comprising at least one quaternized unsaturated ring, are not only suitable for use as couplers for oxidation dyeing, but also make it possible to obtain dye compositions which provide at least one of intense colorations in a very wide range of shades and excellent properties of resistance to the various treatments to which the keratin fibres may be subjected.
A subject of the invention is thus a composition for dyeing keratin fibres, such as, for example, human keratin fibres such as the hair, wherein the composition comprises, in a medium which is suitable for dyeing:
(i) at least one oxidation base; and
(ii)at least one coupler chosen from indolizine derivatives of formula (I) and the acid addition salts thereof: 
in which:
n may be an integer from 0 to 4;
R1 and R3, which may be identical or different, are each chosen from hydrogen atoms; halogen atoms; Z groups; C1-C4 alkyl radicals; C1-C4 alkoxy radicals; C1-C4 monohydroxyalkyl radicals; C2-C4 polyhydroxyalkyl radicals; C1-C4 aminoalkyl radicals; acetylamino radicals; acetylamino-(C1-C4)alkyl radicals; (C1-C4)alkoxy(C1-C4)alkyl radicals; mono(C1-C4)alkylamino(C1-C4)alkyl radicals; di(C1-C4)alkylamino(C1-C4)alkyl radicals; aminocarboxy(C1-C4)alkyl radicals; acetyl(C1-C4)alkylamino(C1-C4)alkyl radicals; and aromatic rings which are optionally substituted with at least one radical chosen from halogen atoms, C1-C4 alkyl radicals, trifluoro-methyl radicals, C1-C4 alkoxy radicals, amino radicals, mono- and disubstituted amino radicals wherein the substituent is chosen from C1-C4 alkyl radicals, (C1-C4)alkylamino(C1-C4)alkyl radicals, di(C1-C4)alkylamino(C1-C4)alkyl radicals, carboxyl radicals and sulphoxy radicals;
R3 may optionally further be chosen from 5- and 6-membered unsaturated heterocycles;
R2 and R4, which may be identical or different, are each chosen from hydrogen atoms; halogen atoms, Z groups; C1-C4 alkyl radicals, C1-C4 monohydroxyalkyl radicals, C2-C4 polyhydroxyalkyl radicals, C1-C4 aminoalkyl radicals, mono(C1-C4)-alkylamino(C1-C4)alkyl radicals, di(C1-C4)alkyl-amino(C1-C4)alkyl radicals, carboxyl radicals, cyano radicals, carboxy(C1-C4)alkyl radicals, nitro radicals and 5- and 6-membered aromatic rings which are optionally substituted with at least one radical chosen from halogen atoms, C1-C4 alkyl radicals, trifluoromethyl radicals, C1-C4 alkoxy radicals, amino radicals and mono- and disubstituted amino radicals wherein the substituent is chosen from C1-C4 alkyl radicals, (C1-C4)alkylamino-(C1-C4)alkyl radicals, di(C1-C4)alkylamino-(C1-C4)alkyl radicals, carboxyl radicals and sulphoxy radicals;
Z is chosen from the following unsaturated cationic groups of formulae (II) and (III) below, and the saturated cationic groups of formula (IV) below: 
in which:
D is a linker arm which is chosen from linear and branched alkylene chains, preferably containing from 1 to 14 carbon atoms, which may be interrupted by at least one hetero atom, and which may be substituted with at least one substituent chosen from hydroxyl and C1-C6 alkoxy radicals, and which may bear at least one ketone function;
the ring members E, G, J, L and M, which may be identical or different, are chosen from carbon, oxygen, sulphur and nitrogen atoms;
b is an integer from 0 to 4;
m is an integer from 0 to 5;
the radicals R, which may be identical or different, are chosen from a second group Z, which may be identical to or different from the first group Z, halogen atoms, hydroxyl radicals, C1-C6 alkyl radicals, C1-C6 monohydroxyalkyl radicals, C2-C6 polyhydroxyalkyl radicals, nitro radicals, cyano radicals, cyano(C1-C6)alkyl radicals, C1-C6 alkoxy radicals, tri(C1-C6)alkylsilane(C1-C6)alkyl radicals, amido radicals, aldehydo radicals, carboxyl radicals, (C1-C6)alkylcarbonyl radicals, thio radicals, C1-C6 thioalkyl radicals, C1-C6 alkylthio radicals, amino radicals, amino radicals protected with at least one group chosen from (C1-C6)alkylcarbonyls, carbamyls and C1-C6 alkylsulphonyl radicals; NHRxe2x80x3 and NRxe2x80x2Rxe2x80x3 groups in which Rxe2x80x3 and Rxe2x80x2xe2x80x3, which may be identical or different, are chosen from C1-C6 alkyl radicals, C1-C6 monohydroxyalkyl radicals and C2-C6 polyhydroxyalkyl radicals;
R5 is chosen from C1-C6 alkyl radicals, C1-C6 mono-hydroxyalkyl radicals, C2-C6 polyhydroxyalkyl radicals, cyano(C1-C6)alkyl radicals, tri(C1-C6)-alkylsilane(C1-C6)alkyl radicals, (C1-C6)alkoxy-(C1-C6)alkyl radicals, carbamyl(C1-C6)alkyl radicals, (C1-C6)alkylcarboxy(C1-C6)alkyl radicals, benzyl radicals and second Z groups which may be identical to or different from the first Z groups;
R6, R7 and R8, which may be identical or different, are each chosen from C1-C6 alkyl radicals, C1-C6 monohydroxyalkyl radicals, C2-C6 polyhydroxyalkyl radicals, (C1-C6)alkoxy(C1-C6)alkyl radicals, cyano(C1-C6)alkyl radicals, aryl radicals, benzyl radicals, amido(C1-C6)alkyl radicals, tri(C1-C6)alkylsilane(C1-C6)alkyl radicals and C1-C6 aminoalkyl radicals in which the amine is protected with at least one group chosen from (C1-C6)alkylcarbonyls, carbamyls and C1-C6 alkylsulphonyl radicals; two of the radicals R6, R7 and R8, may also form, together with the nitrogen atom to which they are attached, 5- and 6-membered saturated carbon-based rings and rings containing at least one hetero atom, such as, for example, a pyrrolidine ring, a piperidine ring, a piperazine ring or a morpholine ring, it being possible for the said ring to be optionally substituted with at least one substituent chosen from halogen atoms, hydroxyl radicals, C1-C6 alkyl radicals, C1-C6 monohydroxyalkyl radicals, C2-C6 polyhydroxyalkyl radicals, nitro radicals, cyano radicals, cyano(C1-C6)alkyl radicals, C1-C6 alkoxy radicals, tri(C1-C6)alkylsilane(C1-C6)alkyl radicals, amido radicals, aldehydo radicals, carboxyl radicals, keto(C1-C6)alkyl radicals, thio radicals, C1-C6 thioalkyl radicals, C1-C6 alkylthio radicals, amino radicals and amino radical protected with at least one group chosen from (C1-C6)alkylcarbonyls, carbamyls and C1-C6 alkylsulphonyl radicals;
one of the radicals R6, R7 and R8 may optionally be chosen from second Z groups, which may be identical to or different from the first Z groups;
R9 is chosen from C1-C6 alkyl radicals; C1-C6 monohydroxyalkyl radicals; C2-C6 polyhydroxyalkyl radicals; aryl radicals; benzyl radicals; C1-C6 aminoalkyl radicals, C1-C6 aminoalkyl radicals wherein the amine is protected by at least one group chosen from (C1-C6)alkylcarbonyls, carbamyls and C1-C6 alkylsulphonyl radicals; carboxy(C1-C6)alkyl radicals; cyano(C1-C6)alkyl radicals; carbamyl(C1-C6)alkyl radicals; C1-C6 trifluoroalkyl radicals; tri(C1-C6)alkylsilane(C1-C6)alkyl radicals; sulphonamido(C1-C6)alkyl radicals; (C1-C6)alkylcarboxy(C1-C6)alkyl radicals; (C1-C6)alkylsulphinyl(C1-C6)alkyl radicals; (C1-C6)alkylsulphonyl(C1-C6)alkyl radicals; (C1-C6)alkylketo(C1-C6)alkyl radicals; N-(C1-C6)alkylcarbamyl(C1-C6)alkyl radicals; and N-(C1-C6)alkylsulphonamido(C1-C6)alkyl radicals;
a and y are integers equal to 0 or 1; with the following provisos:
in the unsaturated cationic groups of formula (II):
when a=0, the linker arm D is attached to the nitrogen atom,
when a=1, the linker arm D is attached to one of the ring members E, G, J and L,
y cannot take the value 1 except:
1) when the ring members E, G, J and L simultaneously represent a carbon atom, and when the radical R5 is attached to the nitrogen atom of the unsaturated ring; or alternatively
2) when at least one of the ring members E, G, J and L represents a nitrogen atom to which the radical R5 is attached;
when b is at least 2, two adjacent radicals R may also form together a ring chosen from unsaturated 5- and 6-membered carbon-based rings and rings containing at least one hetero atom;
in the unsaturated cationic groups of formula (III):
when a=0, the linker arm D is attached to the nitrogen atom,
when a=1, the linker arm D is attached to one of the ring members E, G, J, L and M,
y cannot take the value 1 except when at least one of the ring members E, G, J, L and M represents a divalent atom, and when the radical R5 is attached to the nitrogen atom of the unsaturated ring;
when m is at least 2, two adjacent radicals R may also form together unsaturated 5- and 6-membered carbon-based rings and rings containing at least one hetero atom;
in the cationic groups of formula (IV):
when a=0, the linker arm D is attached to the nitrogen atom bearing the radicals R6 to R8,
when a=1, two of the radicals R6 to R8 form, together with the nitrogen atom to which they are attached, saturated 5- and 6-membered rings as defined above, and the linker arm D is attached to a carbon atom of the said saturated ring;
Xxe2x88x92 is chosen from monovalent and divalent anions and may be chosen, for example, from halides such as chloride, bromide, fluoride and iodide, hydroxides, hydrogen sulphates and C1-C6 alkyl sulphates such as, for example, methyl sulphates and ethyl sulphates;
it being understood that:
at least one of the radicals R1 and R3 represents a hydrogen atom; and
the number of cationic groups Z is at least equal to 1.
Colorations obtained using the inventive dye compositions may possess at least one of the following desirable characteristics: unselectivity, powerful, enable a variety of shades, and excellent properties of resistance to at least one of atmospheric agents chosen from light and bad weather, perspiration and treatments to which the hair may be subjected (such as shampooing, permanent-waving, etc.).
As used herein, xe2x80x9cat least onexe2x80x9d means one or more and thus includes individual components as well as mixtures/combinations. Further, as used herein, unless otherwise noted, alkyl radicals may be chosen from substituted, unsubstituted, linear, branched, and cyclic alkyl radicals. Similarly, as used herein and unless otherwise noted, the alkyl radicals of alkoxy radicals may be chosen from substituted, unsubstituted, linear, branched, and cyclic alkyl radicals.
Non-limiting examples of aromatic rings of formula (I) include phenyl rings, nitrophenyl rings, alkylphenyl rings, alkoxyphenyl rings, polyalkyl-phenylrings and polyalkoxyphenyl rings.
Non-limiting examples of unsaturated 5- and 6-membered heterocycles, such as may be represented by R3, include pyrrole rings, pyridine rings, pyrimidine rings, imidazole rings, pyrazole rings, oxazole rings, thiazole rings, triazole rings, pyrazolotriazole rings, pyrazoloimidazole rings, pyrrolotriazole rings, pyrazolopyrimidine rings, pyrazolopyridine rings, benzimidazole rings, benzoxazole rings, benzothiazole rings, indole rings, indoline rings, indolidine rings, isoindolidine rings, benzotriazoline rings, pyrazine rings, oxazine rings, triazine rings, quinoline rings, tetrahydro-quinoline rings, benzimidazolidine rings and benzopyrimidine rings.
Non-limiting examples of unsaturated group Z rings of formula (II) include pyrrole rings, imidazole rings, pyrazole rings, oxazole rings, thiazole rings, triazole rings, pyrazoltri-azolinium rings, pyrazoloimidazolinium rings, pyrrolotriazolinium rings, pyrazolopyrimidinium rings, pyrazolopyridinium rings, benzimidazolinium rings, benzoxazolinium rings, benzothiazolinium rings, indolinium rings, indolidinium rings, isoindolinium rings, indazolinium rings and benzotriazolinium rings.
Non-limiting examples of unsaturated group Z rings of formula (III) include pyridine rings, pyrimidine rings, pyrazine rings, oxazine rings, triazine rings, quinolinium rings and tetrahydroquinolinium rings.
Non-limiting examples of the compounds of formula (I) include:
N,N-dimethyl-2-phenyl-N-(phenylmethyl)-1-indolizinepropanaminium;
N,N,N-trimethyl-2-phenyl-1-indolizinethanaminium
N,N,N-trimethyl-2-phenyl-1-indolizinepropanaminium bromide;
4-methyl-4-[2-(2-phenyl-1-indolizinyl)ethyl]morpholinium bromide;
N,N-dimethyl-2-phenyl-N-(phenylmethyl)-1-indolizinepropanaminium nitrate;
N,N-dimethyl-2-phenyl-N-(phenylmethyl)-1-indolizinepropanaminium chloride;
N,N,N-trimethyl-2-phenyl-1-indolizinethanaminium methyl sulphate;
trimethyl[2-(2-phenyl-1-indolizinyl)ethyl]ammonium iodide;
trimethyl[2-(2-phenyl-1-indolizinyl)ethyl]ammonium bromide;
1-methyl-2-[2-(7-methyl-2-phenylindolizin-3-yl)ethyl]pyridinium methyl sulphate;
3-methyl-1-[2-(7-methyl-2-phenylindolizin-3-yl)-2-oxoethyl]-3H-imidazol-1-ium chloride;
3-methyl-1-[2-(2-methylindolizin-3-yl)-2-oxoethyl]-3H-imidazol-1-ium chloride;
1-{2-[2-(4-methoxyphenyl)-8-methylindolizin-3-yl]-2-oxoethyl}-3-methyl-3H-imidazol-1-ium chloride;
3-methyl-1-{2-[8-methyl-2-(3-nitrophenyl)indolizin-3-yl]-2-oxoethyl}-3H-imidazol-1-ium chloride;
1-{2-[2-(3-nitrophenyl)indolizin-3-yl]-2-oxoethyl}pyridinium chloride;
1-[2-oxo-2-(2-phenylindolizin-3-yl)ethyl]pyridinium chloride;
1-[2-oxo-2-(2-m-tolylindolizin-3-yl)ethyl]pyridinium chloride;
1-[2-(8,1-{2-[2-(4-methoxyphenyl)-8-methylindolizin-3-yl]-2-oxoethyl}-2-methylpyridinium chloride;
2-phenylindolizin-3-yl)-2-oxoethyl]pyridinium methyl chloride;
[2-(8-methyl-2-phenylindolizin-3-yl)-2-oxoethyl] pyridinium chloride;
2-methyl-1-{2-[2-(3-nitrophenyl)indolizin-3-yl]-2-oxoethyl}pyridinium chloride;
2-methyl-1-[2-oxo-2-(2-phenylindolizin-3-yl)ethyl]pyridinium chloride;
2-methyl-1-{2-[8-methyl-2-(3-nitrophenyl)indolizin-3-yl]-2-oxoethyl}pyridinium chloride;
2-methyl-1-[2-(8-methyl-2-phenylindolizin-3-yl )-2-oxoethyl]pyridinium chloride;
3-methoxycarbonyl-1-{2-[2-(3-nitrophenyl)indolizin-3-yl]-2-oxoethyl}pyridinium chloride;
3-methoxycarbonyl-1-[2-oxo-2-(2-phenylindolizin-3-yl)ethyl] pyridinium chloride;
3-methoxycarbonyl-1-{2-[2-(4-methoxyphenyl)-8-methylindolizin-3-yl]-2-oxoethyl}pyridinium chloride;
3-methoxycarbonyl-1-(2-[8-methyl-2-(3-nitrophenyl)indolizin-3-yl]-2-oxoethyl}pyridinium chloride;
3-methoxycarbonyl-1-[2-(8-methyl-2-phenylindolizin-3-yl)-2-oxoethyl] pyridinium chloride; and the acid addition salts thereof.
According to the present invention, the at least one coupler may be present in the composition in an amount generally ranging from 0.0005% to 12% by weight relative to the total weight of the dye composition, such as from 0.005% to 6% by weight.
The nature of the at least one oxidation base used in the present invention may not be critical. In one embodiment, the at least one oxidation base is chosen from para-phenylenediamines, double bases, para-aminophenols, ortho-aminophenols, heterocyclic oxidation bases, and the acid addition salts of any of the foregoing.
Non-limiting examples of para-phenylenediamines which can be used as the at least one oxidation base include compounds of formula (V) and the acid addition salts thereof: 
wherein:
R10 is chosen from a hydrogen atom, C1-C4 alkyl radicals, C1-C4 monohydroxyalkyl radicals, C2-C4 polyhydroxyalkyl radicals, (C1-C4)alkoxy(C1-C4)alkyl radicals, C1-C4 alkyl radicals substituted with at least one radical chosen from nitrogen-containing radicals, phenyl radicals and 4xe2x80x2-aminophenyl radicals;
R11 is chosen from a hydrogen atom, C1-C4 alkyl radicals, C1-C4 monohydroxyalkyl radicals, C2-C4 polyhydroxyalkyl radicals, (C1-C4)alkoxy(C1-C4)alkyl radicals and C1-C4 alkyl radicals substituted with at least one nitrogen-containing radical;
R12 is chosen from a hydrogen atom, halogen atoms such as a chlorine atom, a bromine atom, an iodine atom and a fluorine atom, C1-C4 alkyl radicals, C1-C4 monohydroxyalkyl radicals, C1-C4 hydroxyalkoxy radicals, acetylamino(C1-C4)alkoxy radicals, mesylamino-(C1-C4)alkoxy radicals and carbamoylamino(C1-C4)alkoxy radicals;
R13 is chosen from a hydrogen atom, halogen atoms and C1-C4 alkyl radicals.
Non-limiting examples of nitrogen containing radicals of formula (V) above include amino radicals, mono(C1-C4)alkylamino radicals, di(C1-C4)alkylamino radicals, tri(C1-C4)alkylamino radicals, monohydroxy(C1-C4)alkylamino radicals, imidazolinium radicals and ammonium radicals.
Non-limiting examples of the para-phenylenediamines of formula (V) above include para-phenylenediamine, para-tolylenediamine, 2-chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,5-dimethyl-para-phenylenediamine, N,N-dimethyl-para-phenylenediamine, N,N-diethyl-para-phenylenediamine, N,N-dipropyl-para-phenylenediamine, 4-amino-N,N-diethyl-3-methylaniline, N,N-bis(-hydroxyethyl)-para-phenylenediamine, 4-N,N-bis(-hydroxyethyl)amino-2-methylaniline, 4-N,N-bis(-hydroxyethyl)amino-2-chloroaniline, 2-hydroxyethyl-para-phenylenediamine, 2-fluoro-para-phenylenediamine, 2-isopropyl-para-phenylenediamine, N-(-hydroxypropyl)-para-phenylenediamine, 2-hydroxymethyl-para-phenylenediamine, N,N-dimethyl-3-methyl-para-phenylenediamine, N-ethyl-N-(-hydroxyethyl)-para-phenylenediamine, N-(,-dihydroxy-propyl)-para-phenylenediamine, N-(4xe2x80x2-aminophenyl)-para-phenylenediamine, N-phenyl-para-phenylenediamine, 2-hydroxyethyloxy-para-phenylenediamine, 2-acetylamino-ethyloxy-para-phenylenediamine and N-(-methoxyethyl)-para-phenylenediamine, and acid addition salts of any of the foregoing.
In one embodiment, para-phenylenediamines of formula (V) above are chosen from para-phenylenediamine, para-tolylenediamine, 2-isopropyl-para-phenylenediamine, 2-hydroxyethyl-para-phenylenediamine, 2-hydroxyethyloxy-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, N,N-bis(-hydroxyethyl)-para-phenylenediamine, 2-chloro-para-phenylenediamine and 2-acetylaminoethyloxy-para-phenylenediamine, and the acid addition salts of any of the foregoing.
As used herein, xe2x80x9cdouble basesxe2x80x9d means compounds comprising at least two aromatic entities substituted with at least one radical chosen from amino radicals and hydroxyl radicals.
Non-limiting examples of double bases which may be used as the at least one oxidation base according to the present invention include compounds of formula (VI) and the acid addition salts thereof: 
in which:
B1 and B2, which may be identical or different, are each chosen from hydroxyl radicals and xe2x80x94NH2 radicals, optionally substituted with at least one radical chosen from C1-C4 alkyl radicals and linker arms Y;
linker arm Y is chosen from linear and branched divalent alkylene chains comprising from 1 to 14 carbon atoms, wherein said divalent alkylene chains may optionally be interrupted by at least one nitrogen-containing radical and optionally interrupted by at least one hetero atom such as an oxygen atom, a sulphur atom or a nitrogen atom, further wherein said divalent alkylene chains may optionally be terminated with at least one nitrogen-containing radical and optionally interrupted by at least one heteroatom such as an oxygen atom, a sulphur atom or a nitrogen atom, and further wherein said divalent alkylene chains may optionally be substituted with at least one radical chosen from hydroxyl radicals and C1-C6 alkoxy radicals;
R14 and R15, which may be identical or different, are each chosen from a hydrogen atom, halogen atoms, C1-C4 alkyl radicals, C1-C4 monohydroxyalkyl radicals, C2-C4 polyhydroxyalkyl radicals, C1-C4 aminoalkyl radicals and linker arms Y;
R16, R17, R18, R19, R20 and R21, which may be identical or different, are each chosen from a hydrogen atom, linker arms Y and C1-C4 alkyl radicals;
with the proviso that only one linker arm Y is present in each compound of formula (III).
Non-limiting examples of double bases of formula (VI)include N,Nxe2x80x2-bis(xcex2-hydroxyethyl)-N,Nxe2x80x2-bis(4xe2x80x2-aminophenyl)-1,3-diaminopropanol, N,Nxe2x80x2-bis(xcex2-hydroxyethyl)-N,Nxe2x80x2-bis(4xe2x80x2-aminophenyl)ethylenediamine, N,Nxe2x80x2-bis(4-aminophenyl)tetramethylenediamine, N,Nxe2x80x2-bis(xcex2-hydroxyethyl)-N,Nxe2x80x2-bis(4-aminophenyl)tetramethylenediamine, N,Nxe2x80x2-bis(4-methylaminophenyl)tetramethylenediamine, N,Nxe2x80x2-bis(ethyl)-N,Nxe2x80x2-bis(4xe2x80x2-amino-3xe2x80x2-methyl-phenyl)ethylenediamine, 1,8-bis(2,5-diaminophenoxy)-3,5-dioxaoctane, and the acid addition salts of any of the foregoing.
In one embodiment, double bases of formula (VI)are chosen from N,Nxe2x80x2-bis(xcex2-hydroxyethyl)-N,Nxe2x80x2-bis(4xe2x80x2-aminophenyl)-1,3-diaminopropanol, 1,8-bis(2,5-diaminophenoxy)-3,5-dioxaoctane and the acid addition salts of any of the foregoing.
Non-limiting examples of para-aminophenols which may be used according to the present invention include compounds of formula (VII) and the acid addition salts thereof: 
wherein:
R22 is chosen from a hydrogen atom, halogen atoms, C1-C4 alkyl radicals, C1-C4 monohydroxyalkyl radicals, (C1-C4)alkoxy(C1-C4)alkyl radicals, C1-C4 aminoalkyl radicals and hydroxy(C1-C4)alkylamino(C1-C4)alkyl radicals; and
R23 is chosen from a hydrogen atom, halogen atoms, C1-C4 alkyl radicals, C1-C4 monohydroxyalkyl radicals, C2-C4 polyhydroxyalkyl radicals, C1-C4 aminoalkyl radicals, cyano(C1-C4)alkyl radicals and (C1-C4)alkoxy(C1-C4)alkyl radicals,
with the proviso that at least one of R22 and R23 is a hydrogen atom.
Non-limiting examples of para-aminophenols of formula (VII) include para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2-(xcex2-hydroxyethylaminomethyl)phenol, 4-amino-2-fluorophenol and the acid addition salts of any of the foregoing.
Non-limiting examples of ortho-aminophenols which may be used as the at least one oxidation base include 2-aminophenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol, 5-acetamido-2-aminophenol and the acid addition salts of any of the foregoing.
Non-limiting examples of heterocyclic bases which may be used as the at least one oxidation base include pyridine derivatives, pyrimidine derivatives, pyrazole derivatives and the acid addition salts of any of the foregoing.
Non-limiting examples of pyridine derivatives include compounds disclosed, for example, in British Patents GB 1 026 978 and GB 1 153 196, the disclosures of which are incorporated herein by reference, such as 2,5-diaminopyridine, 2-(4-methoxyphenyl)amino-3-aminopyridine, 2,3-diamino-6-methoxypyridine, 2-(xcex2-methoxyethyl)amino-3-amino-6-methoxypyridine, 3,4-diaminopyridine and the acid addition salts of any of the foregoing.
Non-limiting examples of pyrimidine derivatives include compounds described, for example, in German Patent DE 2 359 399, Japanese Patents JP 88-169 571 and JP 91-10659, and Patent Application WO 96/15765, the disclosures of which are incorporated herein by reference, such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine, and pyrazolopyrimidine derivatives such as those mentioned in patent application FR-A-2 750 048, the disclosure of which is incorporated herein by reference, such as pyrazolo[1,5-a]pyrimidine-3,7-diamine, 2,5-dimethylpyrazolo[1,5-a]pyrimidine-3,7-diamine, pyrazolo[1,5-a]pyrimidine-3,5-diamine, 2,7-dimethylpyrazolo[1 ,5-a]pyrimidine-3,5-diamine, 3-aminopyrazolo[1 ,5-a]pyrimidin-7-ol, 3-aminopyrazolo[1,5-a]pyrimidin-5-ol, 2-(3-aminopyrazolo[1,5-a]pyrimidin-7-ylamino)ethanol, 2-(7-aminopyrazolo[1,5-a]pyrimidin-3-ylamino)ethanol, 2-[(3-aminopyrazolo[1,5-a]pyrimidin-7-yl)(2-hydroxyethyl)amino]ethanol, 2-[(7-aminopyrazolo[1,5-a]pyrimidin-3-yl)(2-hydroxyethyl)amino]ethanol, 5,6-dimethylpyrazolo[1,5-a]pyrimidine-3,7-diamine, 2,6-dimethylpyrazolo[1,5-a]pyrimidine-3,7-diamine, 2,5,N7,N7-tetramethylpyrazolo[1,5-a]pyrimidine-3,7-diamine, 3-amino-5-methyl-7-imidazolylpropylaminopyrazolo[1,5-a]pyrimidine, and the addition salts, tautomeric forms, (when a tautomeric equilibrium exists) and acid addition salts of any of the foregoing.
Further non-limiting examples of pyrazole derivatives include compounds described in German Patents DE 3 843 892 and DE 4 133 957 and Patent Applications WO 94/08969, WO 94/08970, FR-A-2 733 749 and DE 195 43 988, the disclosures of which are incorporated hereby by reference, such as 4,5-diamino-1-methylpyrazole, 3,4-diaminopyrazole, 4,5-diamino-1-(4xe2x80x2-chlorobenzyl)pyrazole, 4,5-diamino-1-(xcex2-hydroxy-ethyl)pyrazole, 4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazinopyrazole, 1-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-1-methylpyrazole, 4,5-diamino-1-tert-butyl-3-methylpyrazole, 4,5-diamino-1-(xcex2-hydroxyethyl)-3-methylpyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl-3-(4xe2x80x2-methoxyphenyl)pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-1-methylpyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole, 4,5-diamino-3-methyl-1-isopropylpyrazole, 4-amino-5-(2xe2x80x2-aminoethyl)amino-1,3-dimethylpyrazole, 3,4,5-triaminopyrazole, 1-methyl-3,4,5-triaminopyrazole, 3,5-diamino-1-methyl-4-methylamino-pyrazole, 3,5-diamino-4-(xcex2-hydroxyethyl)amino-1-methylpyrazole, and the acid addition salts of any of the foregoing.
According to the present invention, the at least one oxidation base may be present in the composition in an amount generally ranging from 0.0005% to 12% by weight relative to the total weight of the dye composition, such as from 0.005% to 6% by weight.
The dye composition according to the present invention may optionally further comprise at least one additional coupler different from the indolizine derivatives of formula (I) and may optionally further comprise at least one direct dye, for example, to vary and/or enrich the shade obtained using the at least one oxidation base with highlights.
The at least one additional coupler which can be used in the dye composition according to with the present invention may be chosen from couplers, such as, for example, meta-phenylenediamines, meta-aminophenols, meta-diphenols and heterocyclic couplers such as, for example, indole derivatives, indoline derivatives, benzimidazole derivatives, benzomorpholine derivatives, sesamol derivatives, pyridine derivatives, pyrimidine derivatives, pyrazole derivatives and the acid addition salts thereof.
In one embodiment, the at least one additional coupler is chosen from 2-methyl-5-aminophenol, 5-N-(xcex2-hydroxyethyl)amino-2-methylphenol, 3-aminophenol, 1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene, 4-chloro-1,3-dihydroxybenzene, 2,4-diamino-1-(xcex2-hydroxyethyloxy)benzene, 2-amino-4-(xcex2-hydroxyethylamino)-1-methoxybenzene, 1,3-diaminobenzene, 1,3-bis(2,4-diaminophenoxy)propane, sesamol, 1-amino-2-methoxy-4,5-methylenedioxybenzene, xcex1-naphthol, 2-methyl-1-naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole, 6-hydroxyindoline, 2,6-dihydroxy-4-methylpyridine, 1-H-3-methylpyrazol-5-one, 1-phenyl-3-methylpyrazol-5-one and the addition salts of any of the foregoing.
When present, the at least one additional coupler may be present in the composition in an amount generally ranging 0.0001% to 10% by weight relative to the total weight of the dye composition, such as from 0.005% to 5% by weight.
According to the present invention, the acid addition salts may be chosen from hydrochlorides, hydrobromides, sulphates, tartrates, lactates and acetates.
The medium suitable for oxidation dyeing, or support, according to the present invention may be chosen from water and a mixture of water and at least one organic solvent in order to dissolve the compounds which might not be sufficiently soluble in water alone. Non-limiting examples of the at least one organic solvent includes C1-C4 alkanols such as ethanol and isopropanol; glycerol; glycols and glycol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol, diethylene glycol monomethyl ether; aromatic alcohols such as benzyl alcohol and phenoxyethanol; and analogous solvents.
According to the present invention, the at least one organic solvent maybe present in the composition in an amount generally ranging from 1% to 40% by weight relative to the total weight of the dye composition, such as from 5% to 30% by weight.
The pH of the dye composition in accordance with the present invention generally ranges from 3 to 12. It can be adjusted to the desired value by means of at least one agent commonly used in dyeing keratin fibres chosen from acidifying agents and basifying agents.
Non-limiting examples of acidifying agents include inorganic acids and organic acids such as hydrochloric acid, orthophosphoric acid, carboxylic acids (such as tartaric acid, citric acid and lactic acid) and sulphonic acids.
Non-limiting examples of basifying agents include aqueous ammonia, alkaline carbonates, alkanolamines such as mono-, di- and triethanolamines and derivatives thereof, sodium hydroxide, potassium hydroxide and compounds of formula (VIII): 
wherein:
R28 is chosen from divalent propylene residues, optionally substituted with at least one radical chosen from hydroxyl radicals and C1-C4 alkyl radicals; R24, R25, R26 and R27, which may be identical or different, are each chosen from a hydrogen atom, C1-C4 alkyl radicals and C1-C4 hydroxyalkyl radicals.
According to the present invention, the dye composition may further comprise at least one adjuvant chosen from adjuvants conventionally used in hair dyeing compositions, such as anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, zwitterionic surfactants, anionic polymers, cationic polymers, nonionic polymers, amphoteric polymers, zwitterionic polymers, inorganic thickeners, organic thickeners, antioxidants, penetration agents, sequestering agents, fragrances, buffers, dispersing agents, conditioners, such as, for example, silicones, film-forming agents, preserving agents and opacifiers.
Needless to say, a person skilled in the art will take care to choose any optional additional compound(s) such that the advantageous properties associated with the inventive dye compositions are not, or not substantially, adversely affected by the addition(s) envisaged.
According to the present invention, the dye composition may be provided in various forms, such as in the form of a liquid, a cream or a gel, or in any other form suitable for dyeing keratin fibres, such as human hair.
Another subject of the present invention is a process for oxidation dyeing of keratin fibres comprising applying to said keratin fibres for a sufficient time to obtain a desired color at least one dye composition comprising, in a medium suitable for dyeing, (i) at least one coupler chosen from indolizine derivatives of formula (I) and acid addition salts thereofp; and (ii) at least one oxidation base. In one embodiment, the keratin fibres are chosen from human keratin fibres. In another embodiment, the human keratin fibres are hair.
In another embodiment, the at least one dye composition is applied to the keratin fibres, and the desired color may be developed at a pH chosen from acidic, neutral or alkaline pH. Further, the at least one dye composition may further comprise at least one oxidizing agent which may be added to the at least one dye composition at the time of application, and/or which may be present in at least one oxidizing composition. In one embodiment, the at least one oxidizing composition may be applied simultaneously with said at least one dye composition, while in another embodiment, the at least one oxidizing composition may be applied to the keratin fibres sequentially with the at least one dye composition.
In a further embodiment, the at least one dye composition is mixed, at the time of use, with at least one oxidizing composition comprising, in a medium appropriate for dyeing, at least one oxidizing agent present in an amount sufficient to develop a desired coloration. The mixture obtained may subsequently be applied to the keratin fibres and may be left to stand for 3 to 50 minutes, such as for 5 to 30 minutes. In yet another embodiment, the fibres are rinsed, and may optionally be washed with a shampoo, rinsed again and dried.
According to the present invention, the at least one oxidizing agent may be chosen from oxidizing agents conventionally used for the oxidation dyeing of keratin fibres, such as hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulphates, peracids and enzymes such as peroxidases, laccases, tyrosinases and oxidoreductases (such as pyranose oxidases, glucose oxidases, glycerol oxidases, lactate oxidases, pyruvate oxidases and uricases).
The pH of the at least one oxidizing composition comprising the at least one oxidizing agent after mixing with the at least one dye composition may generally range from 3 to 12, such as from 5 and 11. Further, the pH may be adjusted to a desired value by means of at least one agent chosen from acidifying and basifying agents commonly in dyeing keratin fibres and as defined above.
The at least one oxidizing composition as defined above may also contain at least one adjuvant conventionally used in hair dyeing compositions and as defined above.
The composition which is applied to the keratin fibres may be in various forms, such as in the form of a liquid, a cream or a gel or any other form suitable for carrying out dyeing of keratin fibres, such as human hair.
The present invention also provides a multi-compartment device or kit or any other packaging system, comprising a first compartment containing a first composition comprising at least one dye composition as defined above and a second compartment containing a second composition comprising at least one oxidizing composition as defined above. These devices may be equipped with a means allowing the desired mixture to be deposited on the hair, such as the devices described in French Patent FR-2 586 913, the disclosure of which is incorporated herein.
Finally, this invention provides certain novel indolizine derivatives of formula (I). These novel indolizine derivatives, and the acid addition salts thereof, correspond to formula (I) as defined above, with the following additional conditions:
Z cannot be chosen from the cationic groups of formula (IV) as defined above;
providing that 4-methyl-4-[2-(2-phenyl-1-indolizinyl)ethyl]morpholinium bromide is excluded.
The excluded compounds are known in the pharmaceutical field, as seen in patents U.S. Pat. No. 3,717,644 and U.S. Pat. No. 3,642,807.
In one embodiment, these novel indolizine derivatives may be chosen from:
1-methyl-2-[2-(7-methyl-2-phenylindolizin-3-yl)ethyl]pyridinium methyl sulphate;
3-methyl-1-[2-(7-methyl-2-phenylindolizin-3-yl)-2-oxoethyl]-3H-imidazol-1-ium chloride;
3-methyl-1-[2-(2-methylindolizin-3-yl)-2-oxoethyl]-3H-imidazol-1-ium chloride;
1-{2-[2-(4-methoxyphenyl)-8-methylindolizin-3-yl]-2-oxoethyl}-3-methyl-3H-imidazol-1-ium chloride;
3-methyl-1-{2-[8-methyl-2-(3-nitrophenyl)indolizin-3-yl]-2-oxoethyl}-3 H-imidazol-1-ium chloride;
1-{2-[2-(3-nitrophenyl)indolizin-3-yl]-2-oxoethyl}pyridinium chloride;
1-[2-oxo-2-(2-phenylindolizin-3-yl)ethyl]pyridinium chloride;
1-[2-oxo-2-(2-m-tolylindolizin-3-yl)ethyl]pyridinium chloride;
1-[2-(8,1-{2-[2-(4-methoxyphenyl)-8-methylindolizin-3-yl]-2-oxoethyl}-2-methylpyridinium chloride;
2-phenylindolizin-3-yl )-2-oxoethyl]pyridinium methyl chloride;
[2-(8-methyl-2-phenylindolizin-3-yl)-2-oxoethyl] pyridinium chloride;
2-methyl-1-{2-[2-(3-nitrophenyl)indolizin-3-yl]-2-oxoethyl}pyridinium chloride;
2-methyl-1-[2-oxo-2-(2-phenylindolizin-3-yl)ethyl]pyridinium chloride;
2-methyl-1-{2-[8-methyl-2-(3-nitrophenyl)indolizin-3-yl]-2-oxoethyl}pyridinium chloride;
2-methyl-1-[2-(8-methyl-2-phenylindolizin-3-yl)-2-oxoethyl]pyridinium chloride;
3-methoxycarbonyl-1-{2-[2-(3-nitrophenyl)indolizin-3-yl]-2-oxoethyl}pyridinium chloride;
3-methoxycarbonyl-1-[2-oxo-2-(2-phenylindolizin-3-yl)ethyl]pyridinium chloride;
3-methoxycarbonyl-1-{2-[2-(4-methoxyphenyl)-8-methylindolizin-3-yl]-2-oxoethyl}pyridinium chloride;
3-methoxycarbonyl-1-{2-[8-methyl-2-(3-nitropheny)indolizin-3-yl]-2-oxoethyl}pyridinium chloride;
3-methoxycarbonyl-1-[2-(8-methyl-2-phenylindolizin-3-yl)-2-oxoethyl]pyridinium chloride;
and the acid addition salts of any of the foregoing. The addition salts with an acid of the above novel compounds are chosen from those defined above for the compounds of formula (I).
These specific compounds may be prepared according to the synthetic process of indolizines comprising the step of reacting compounds chosen from alkyl-2 pyridine and aralkyl-2 pyridine with a haloacetone thus producing a pyridinium salt (Chichibabin, Ber. 1927, 60, 1607; Borrows, Holland, Kenyon, J. Chem. Soc. 1946, 1069). By reacting the salt with a base such as sodium bicarbonate in aqueous medium, indolinine is produced by cyclisation. Other methods for producing the indolizine nucleus are disclosed in T. Uchida et K. Matsumoto, Synthesis, 1976, 209-236. These compounds are then quaternized according to known conventional quaternization methods.
The compounds thus obtained can be purified by known methods such as distillation and crystallisation.
Other than in the operating example, or where otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, and so forth used in the specification and claims are to be understood as being modified in all instances by the term xe2x80x9cabout.xe2x80x9d Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should be construed in light of the number of significant digits and ordinary rounding approaches.
Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contain certain errors necessarily resulting from the standard deviation found in their respective testing measurements. The following examples are intended to illustrate the invention without limiting the scope as a result.